JP3874361B2 - Ozone generation method and apparatus using heteropolar crystal - Google Patents

Ozone generation method and apparatus using heteropolar crystal Download PDF

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JP3874361B2
JP3874361B2 JP2005151900A JP2005151900A JP3874361B2 JP 3874361 B2 JP3874361 B2 JP 3874361B2 JP 2005151900 A JP2005151900 A JP 2005151900A JP 2005151900 A JP2005151900 A JP 2005151900A JP 3874361 B2 JP3874361 B2 JP 3874361B2
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crystal
atmosphere
ozone
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JP2006327856A (en
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嘉昭 伊藤
進三 吉門
義一 中西
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Kyoto University
Doshisha Co Ltd
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Doshisha Co Ltd
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    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/10—Preparation of ozone

Description

この発明は、異極像結晶を熱励起することによって結晶の回りに発生する高電界を利用して、大気中でオゾンを生成させる方法および装置に関するもので、特に常圧雰囲気中に高濃度のオゾンを発生させる手段を提供するものである。   The present invention relates to a method and apparatus for generating ozone in the atmosphere by utilizing a high electric field generated around a crystal by thermally exciting a heteropolar image crystal, and in particular, a high concentration in an atmospheric pressure atmosphere. A means for generating ozone is provided.

本発明者等は、３〜６Ｐａ程度の真空ないし低気体圧雰囲気中に焦電結晶として知られているニオブ酸リチウム（LiNbO3）単結晶などの異極像結晶体を配置し、これに周期的に温度変化を与えることによって、結晶表面で電荷の相殺に追随できないために表面に生じた電子を含む荷電粒子をターゲットあるいは異極像結晶に衝突させてＸ線を発生させる装置を発明し（特願２００３−４０７９８５、２００４−９８３７１）、このＸ線をベリリウム窓などを通して酸素を含む気流中に照射してオゾンを発生させる装置を発明（特願２００４−９９０６９）した。さらにこの真空筐体内に異極像結晶体とともに熱電子を発生する電子銃を併設し、これからの熱電子を結晶体の温度変化によって生じた高電界を利用してＸ線ターゲットへ指向衝突させ、ターゲットからの制動輻射による強力Ｘ線によってより効率的にオゾンを発生させる装置も発明（特願２００５−９４７４２）した。
特願２００３−４０７９８５ 特願２００４−９８３７１ 特願２００４−９９０６９ 特願２００５−９４７４２ The present inventors have placed a heteropolar image crystal such as a lithium niobate (LiNbO 3 ) single crystal known as pyroelectric crystal in a vacuum or low gas pressure atmosphere of about 3 to 6 Pa, and has a periodicity on it. Invented an apparatus for generating X-rays by causing charged particles containing electrons generated on the surface to collide with the target or the heteropolar crystal because the temperature change is not allowed to follow the charge cancellation on the crystal surface. Japanese Patent Application Nos. 2003-407985 and 2004-98371) have invented an apparatus for generating ozone by irradiating X-rays into a gas stream containing oxygen through a beryllium window or the like (Japanese Patent Application No. 2004-99069). Furthermore, an electron gun that generates thermoelectrons together with the heteropolar image crystal body is provided in the vacuum casing, and the thermal electrons from this are directed to the X-ray target using a high electric field generated by the temperature change of the crystal body, A device for generating ozone more efficiently by intense X-rays generated by braking radiation from the target was also invented (Japanese Patent Application No. 2005-94742).
Japanese Patent Application No. 2003-407985 Japanese Patent Application No. 2004-98371 Japanese Patent Application No. 2004-99069 Japanese Patent Application No. 2005-94742

この発明は、前記異極像結晶の熱励起による熱イオン効果や荷電粒子の挙動について研究を進めた結果、大気圧ないしそれ以上の高圧気体雰囲気中においても、異極像結晶周辺の大気を直接オゾン化し得る手段を開発したもので、高圧電源や真空設備などを必要としないで大気中で簡単に高濃度のオゾンを生成できる方法及び装置を提供するものである。   As a result of research on the thermionic effect caused by the thermal excitation of the heteropolar image crystal and the behavior of charged particles, the present invention has made it possible to directly irradiate the atmosphere around the heteropolar image crystal even in a high-pressure gas atmosphere of atmospheric pressure or higher. The present invention provides a method and apparatus for developing ozone that can easily generate high-concentration ozone in the atmosphere without requiring a high-voltage power supply or vacuum equipment.

上記課題を解決する第１の発明は、分極方向を揃えた異極像結晶を熱励起することによって、大気中において結晶の回りに高電界を発生させ、前記高電界による気中酸素分子の解離・会合現象、及び結晶周辺荷電粒子の粒子間衝突および結晶への衝突による軟Ｘ線放出と放電現象などの複合効果を利用して、大気中で高濃度のオゾンを発生させる方法である。
第２の発明は、前記気中の荷電粒子や酸素分子の解離・会合などの複合作用を効果的に達成するための筐体構成、結晶の熱励起手段の配置・制御構成を備えたオゾン生成装置を提供する。 According to a first aspect of the present invention for solving the above problems, a high electric field is generated around a crystal in the atmosphere by thermally exciting a heteropolar image crystal having a uniform polarization direction, and dissociation of oxygen molecules in the air by the high electric field. This is a method for generating high-concentration ozone in the atmosphere by utilizing a combined effect such as an association phenomenon and soft X-ray emission and discharge phenomenon due to collision between particles and collision of charged particles around the crystal.
The second invention is the generation of ozone provided with a housing structure for effectively achieving the combined action such as dissociation / association of charged particles and oxygen molecules in the air, and arrangement / control structure of the crystal thermal excitation means. Providing equipment.

この発明によれば、真空装置や高電圧電源などの特別な設備を必要とすることなく、また重金属などのＸ線ターゲットも用いないで、簡便に高濃度のオゾンが生成できるので、殺菌消毒など各種のオゾン利用目的に簡便に対応できる外、金属や半導体の酸化等の工業的用途にも広く利用できる。   According to the present invention, high-concentration ozone can be easily generated without requiring special equipment such as a vacuum apparatus or a high-voltage power supply, and without using an X-ray target such as heavy metal. In addition to being able to easily cope with various ozone utilization purposes, it can be widely used for industrial applications such as oxidation of metals and semiconductors.

図１は本発明のオゾン発生方法及び装置の基本概念を示す実験例図で、１は大気を常圧状態で収容する筐体、２はタンタル酸リチウム（LiTaO3）、ニオブ酸リチウム(LiNbO3)などの異極像結晶体で、実験では直径７５ｍｍ厚さ２０ｍｍの円柱状のブロック結晶を使用した。この結晶体は結晶成長させる段階でその分極方向が上面ａが負の極性に揃うように作製した。３はこの結晶体の下面ｂ（分極方向が正に帯電している面）に設置された加熱・冷却ステージで、ペルチエ素子などで構成される。４はこのペルチエ素子への電流制御回路で印加電圧の極性を切り換えることにより結晶体は加熱または冷却される。この加熱・冷却サイクル、加熱温度は制御回路４によって予め定めた条件にプログラム制御される。５は大気圧ガス（空気など）供給管、６はオゾン化されたガスの取り出し管、７はオゾン濃度測定器で導管８、９を介して筐体１内と連通している。１０、１１、１２、１３はそれぞれの管路の開閉弁である。 1 in Experimental Example diagram showing the basic concept of the ozone generating method and apparatus of the present invention, a housing for housing 1 the air at normal pressure, 2 lithium tantalate (LiTaO 3), lithium niobate (LiNbO 3 In the experiment, a cylindrical block crystal having a diameter of 75 mm and a thickness of 20 mm was used. This crystal was produced so that the polarization direction was aligned with the negative polarity of the upper surface a at the stage of crystal growth. Reference numeral 3 denotes a heating / cooling stage installed on the lower surface b (a surface in which the polarization direction is positively charged) of the crystal body, and is composed of a Peltier element or the like. 4 is a current control circuit for the Peltier element, and the crystal is heated or cooled by switching the polarity of the applied voltage. The heating / cooling cycle and the heating temperature are controlled by the control circuit 4 under predetermined conditions. 5 is an atmospheric pressure gas (air etc.) supply pipe, 6 is an ozonized gas take-out pipe, and 7 is an ozone concentration measuring instrument communicating with the inside of the housing 1 via conduits 8 and 9. Reference numerals 10, 11, 12, and 13 denote on-off valves for the respective pipelines.

図の装置では、導管５から筐体内へ供給された空気は循環路８からオゾン測定器７を経て循環路９から再び筐体内へ還流するように構成されており、筐体内のオゾン濃度が所望の濃度になったことを検証した状態で弁１１を開いて、ここから所望濃度のオゾンガスを滅菌室などオゾン処理を行う場所へ供給するようにした例である。   In the apparatus shown in the figure, the air supplied from the conduit 5 into the casing is configured to recirculate from the circulation path 8 through the ozone measuring device 7 to the casing 9 again, and the ozone concentration in the casing is desired. This is an example in which the valve 11 is opened in a state where it is verified that the concentration reaches the desired concentration, and ozone gas having a desired concentration is supplied from here to a place where ozone treatment is performed, such as a sterilization chamber.

図において、筐体内の大気雰囲気中にオゾンを生成させる操作について説明する。
分極方向を揃えた異極像結晶を、その負の電気面ａを上側（大気側）に、正の面ｂを下側（加熱・冷却ステージ側）に向けて設置する。先ずペルチエ素子からなる加熱・冷却ステージ３の発熱面が、異極像結晶体の下面ｂになるように電流を印加し、結晶体２を約２００℃程度まで急速に加熱昇温する。次いでペルチエ素子への印加電流極性を切り換えて素子の吸熱面が結晶のｂ面に対向するようにし、結晶温度を強制的に常温付近まで低下させる。 In the figure, an operation for generating ozone in the air atmosphere in the housing will be described.
A heteropolar image crystal having the same polarization direction is placed with its negative electric surface a facing upward (atmosphere side) and positive surface b facing downward (heating / cooling stage side). First, an electric current is applied so that the heat generation surface of the heating / cooling stage 3 made of a Peltier element becomes the lower surface b of the heteropolar crystal body, and the crystal body 2 is rapidly heated to about 200 ° C. Next, the polarity of the current applied to the Peltier element is switched so that the endothermic surface of the element faces the b-plane of the crystal, and the crystal temperature is forcibly lowered to near room temperature.

この結晶の昇温・降温操作はペルチエ素子への電流制御回路４によって自動的に制御する。例えば最初約３０分弱結晶を加熱し次いで約９０分の間に降温する操作を約２時間のサイクルで繰り返すように制御する。   The temperature raising / lowering operation of the crystal is automatically controlled by the current control circuit 4 to the Peltier element. For example, the operation of first heating the crystal for about 30 minutes and then lowering the temperature for about 90 minutes is controlled to be repeated in a cycle of about 2 hours.

尚図において筐体１は、金属・強化プラスチック・ＦＲＰなど大気圧に耐える適当な部材で構成できるが、オゾンの吸着が少なくオゾンの強酸化性にも耐えうるものが望ましい。   In the figure, the housing 1 can be composed of an appropriate member that can withstand atmospheric pressure, such as metal, reinforced plastic, and FRP. However, it is desirable that the housing 1 can withstand the strong oxidation of ozone with little ozone adsorption.

図２は、上記の操作による筐体１内で生成されたオゾンの濃度をオゾン濃度測定器７によって計測したデータで、縦軸は筐体内のオゾン濃度（ｐｐｂ）、横軸は結晶体の加熱冷却時間（ｈ）を示す。   FIG. 2 is data obtained by measuring the concentration of ozone generated in the housing 1 by the above operation using the ozone concentration measuring device 7. The vertical axis represents the ozone concentration (ppb) in the housing, and the horizontal axis represents the heating of the crystal. The cooling time (h) is shown.

結晶体２を常温からカーブｕに沿って約２００℃まで昇温し、その後カーブｄに沿って常温付近まで温度降下させた場合、カーブの頂点ｐ（２００℃付近）では筐体内のオゾン濃度は６０００ｐｐｂに達することが実証された。即ち約３０分間結晶温度を上昇させる段階でオゾン生成が急速に進行し、その後約９０分間に亘る温度下降段階では筐体内のオゾン濃度が低下することが判明した。
従って高濃度のオゾンを得たいときは、濃度計測値が６０００ｐｐｂになったとき弁１１を開いて出口管６からガスを取り出せばよく、それ以下でもよい場合は加熱開始後１５分から６０分程度まで出口弁１１を開けておけばよいことになる。 When the temperature of the crystalline body 2 is raised from room temperature to about 200 ° C. along the curve u and then lowered to near room temperature along the curve d, the ozone concentration in the casing is at the apex p (around 200 ° C.) of the curve. It has been demonstrated to reach 6000 ppb. In other words, it was found that ozone generation rapidly progressed at the stage where the crystal temperature was raised for about 30 minutes, and the ozone concentration in the casing was lowered at the temperature drop stage for about 90 minutes thereafter.
Therefore, to obtain high-concentration ozone, when the measured concentration value reaches 6000 ppb, it is sufficient to open the valve 11 and take out the gas from the outlet pipe 6. It is sufficient to open the outlet valve 11.

又本発明者等の実験によれば、結晶温度が上昇する過程ｕでオゾン化が進行し温度降下段階ｄではオゾン発生が少ないことも見出した。さらに温度上昇の勾配カーブｕを急峻にする程オゾン生成効率が高くなることも実証した。   Further, according to experiments by the present inventors, it has been found that ozonization proceeds in the process u in which the crystal temperature rises, and ozone generation is small in the temperature drop stage d. It was also demonstrated that the ozone generation efficiency increases as the temperature rise gradient curve u becomes steeper.

次に異極像結晶の温度変化に伴う高電界発生とこれによる大気圧下でのオゾン生成のメカニズムについて説明する。
分極方向を揃えた異極像結晶をその負の電気面を上側（大気側）に、正の面を下側（加熱・冷却ステージ側）に設置した場合について、結晶の温度変化による高電界発生の原理について説明する。 Next, the generation of a high electric field accompanying the temperature change of the heteropolar crystal and the mechanism of ozone generation under atmospheric pressure due to this will be described.
When a negative-polarized crystal with the same polarization direction is installed with its negative electrical surface on the upper side (atmosphere side) and positive surface on the lower side (heating / cooling stage side), a high electric field is generated due to the temperature change of the crystal. The principle will be described.

（１）結晶温度を上昇させると、結晶の分極率が小さくなり負面の負の電荷密度が小さくなる。常温での平衡状態ではこの負面には負電荷と等量の正イオン（プロトン・ヒドロニュウムイオン等）が吸着しており、温度上昇によって熱脱離速度は速くなるが分極率の低下速度の方が速いために、負面は結果的には前記正イオンによって正に帯電する。裏面の正の電気面側では、ステージ３の接地・非接地の如何に拘わらず、平均的には負に帯電する。   (1) When the crystal temperature is raised, the polarizability of the crystal decreases and the negative charge density on the negative surface decreases. In the equilibrium state at room temperature, this negative surface is adsorbed with the same amount of positive ions (proton, hydronium ion, etc.) as the negative charge, and the thermal desorption rate increases with temperature rise, but the rate of decrease in polarizability As a result, the negative surface is positively charged by the positive ions as a result. On the positive electrical surface side of the back surface, the stage 3 is negatively charged on average regardless of whether the stage 3 is grounded or not grounded.

これにより、結晶内では負面（上面ａ）から正の面（下面ｂ）の方向に電気力線が生じ、結晶の外部では負面側から大気に向かって図１の電気力線φに示すように高電界が発生する。この電界は結晶温度の変化が大きい程（温度上昇勾配が大きい程）強い電界となる。   As a result, electric lines of force are generated in the direction from the negative surface (upper surface a) to the positive surface (lower surface b) in the crystal, and as indicated by electric force lines φ in FIG. A high electric field is generated. This electric field becomes stronger as the change in the crystal temperature is larger (as the temperature rise gradient is larger).

次にこの高電界によるオゾン発生のメカニズムについて説明する。   Next, the mechanism of ozone generation by this high electric field will be described.

（i）この強い電界によって結晶周辺の気体の一部が電離し、遊離した電子が結晶表面に衝突し、その静電エネルギー（運動エネルギーに転化）の大きさに応じた波長の連続Ｘ線および結晶元素の特性Ｘ線が発生する。本発明の場合、筐体内空間は大気圧であるので、前記電子の平均自由行程は短くなり（大気中の場合約７０ｎｍ）、高電界であっても十分加速されない（運動エネルギーは小さい）ため、発生するＸ線の波長は非常に長くなりその大部分は軟Ｘ線となる。   (I) A part of the gas around the crystal is ionized by this strong electric field, the liberated electrons collide with the crystal surface, and continuous X-rays with wavelengths corresponding to the magnitude of the electrostatic energy (converted into kinetic energy) and Characteristic X-rays of crystalline elements are generated. In the case of the present invention, since the space in the housing is atmospheric pressure, the mean free path of the electrons is shortened (about 70 nm in the atmosphere) and is not sufficiently accelerated even in a high electric field (kinetic energy is small). The wavelength of the generated X-ray is very long and most of it is soft X-ray.

この軟Ｘ線が大気中の酸素分子に吸収され酸素分子が解離し、励起された単原子が発生し、これが他の酸素イオンと会合してオゾンを生成する。一般に酸素の光子の吸収は紫外線波長で大きいが、軟Ｘ線の光子はさらに大きいエネルギーを持っており、軟Ｘ線光子１個で複数の酸素分子を励起解離させるので、全体的にはこの軟Ｘ線によってオゾン生成効率が高まり、大気中で高濃度のオゾンを発生させることができる。   This soft X-ray is absorbed by oxygen molecules in the atmosphere and the oxygen molecules are dissociated to generate excited single atoms, which associate with other oxygen ions to generate ozone. In general, absorption of oxygen photons is large at ultraviolet wavelengths, but soft X-ray photons have higher energy, and a single soft X-ray photon excites and dissociates a plurality of oxygen molecules. X-rays increase the ozone generation efficiency and can generate high-concentration ozone in the atmosphere.

この軟Ｘ線は、気体の圧力が高いため大気中でエネルギーは吸収され筐体外へ漏れることはなく、生体への危険性も少ない。   Since the soft X-ray has a high gas pressure, energy is absorbed in the atmosphere and does not leak out of the casing, and there is little danger to the living body.

（ii）また、大気中の酸素分子自体も前記強電界によって解離し、励起された単原子が前記軟Ｘ線とは別に大気中に発生する。この発生した酸素の単原子が他の酸素分子と会合しオゾンを生成する。   (Ii) In addition, oxygen molecules themselves in the atmosphere are also dissociated by the strong electric field, and excited single atoms are generated in the atmosphere separately from the soft X-rays. The generated oxygen single atom associates with other oxygen molecules to generate ozone.

（iii）さらには、上記結晶による高電界によって結晶から熱解離したイオンや電子などの荷電粒子が（熱イオン効果）、結晶周辺のガス分子と衝突し放電が起こる。この放電によって結晶周辺で一種の大気圧プラズマ現象が生じ、大気中の酸素分子のオゾン化が起こるとも考えられる。この放電現象は気体圧が高く荷電粒子の平均自由行程が短いため結晶近辺でのみ発生しこの付近でオゾン化が促される。   (Iii) Furthermore, charged particles such as ions and electrons thermally dissociated from the crystal due to the high electric field generated by the crystal (thermionic effect) collide with gas molecules around the crystal and discharge occurs. It is considered that this discharge causes a kind of atmospheric pressure plasma phenomenon around the crystal, and ozonization of oxygen molecules in the atmosphere occurs. This discharge phenomenon occurs only in the vicinity of the crystal because the gas pressure is high and the mean free path of charged particles is short, and ozonization is promoted in the vicinity.

以上結晶温度の上昇時には、上記（i）（ii）（iii）の複合作用によって大気中でのオゾン化が効率的に進行する。   As described above, when the crystallization temperature rises, ozonization in the air efficiently proceeds by the combined action of (i), (ii), and (iii).

（２）次に結晶温度が降下する過程においても、オゾン化効率は低下するが同様にオゾン発生が起こり得る。即ち   (2) Next, in the process where the crystal temperature is lowered, the ozonization efficiency is lowered, but ozone can be generated in the same manner. That is

（iv）温度降下時は結晶の分極率が大きくなり、負の電気面ではその負の電荷密度が大きくなり平均的にみて負に帯電する。裏側の正の面ではステージの接地の有無に関係なく平均的にみて正に帯電する。従って結晶内では正の面から負面の方向に電気力線（電界）が生じ、空間内では加熱・冷却ステージや筐体金属面の正電荷から結晶の負面に向かって電界が発生する。この電界によって前記同様大気中の気体分子の一部が電離し、この電子が筐体などに衝突してＸ線が発生する。しかし筐体内の圧力が高いためこの電子の飛翔行程は著しく制限され、一部のみが近辺の気体分子と衝突し、これから発生するＸ線によって気体分子が励起されオゾンを生成することになる。しかしその生成量は比較的少ない。   (Iv) When the temperature drops, the polarizability of the crystal increases, and on the negative electrical surface, the negative charge density increases and, on average, is negatively charged. The positive surface on the back side is positively charged on average regardless of whether the stage is grounded or not. Therefore, electric lines of force (electric field) are generated from the positive surface to the negative surface in the crystal, and an electric field is generated in the space from the positive charges on the heating / cooling stage and the casing metal surface toward the negative surface of the crystal. As described above, a part of the gas molecules in the atmosphere is ionized by this electric field, and the electrons collide with the housing or the like to generate X-rays. However, since the pressure in the casing is high, the flight process of electrons is remarkably limited. Only a part of the electrons collides with nearby gas molecules, and the gas molecules are excited by the X-rays to be generated to generate ozone. However, the amount produced is relatively small.

（v）また温度上昇時と同様に、前記高電界によって大気中の酸素分子が解離され、発生した励起状態の単原子が他の酸素イオンと会合しオゾンを生成する。
これにより温度降下時においても若干のオゾン生成が行われるが、図２のグラフでも示されるようにその生成量は少ない。 (V) In the same manner as when the temperature is increased, oxygen molecules in the atmosphere are dissociated by the high electric field, and the generated monoatomic atoms are associated with other oxygen ions to generate ozone.
As a result, a slight amount of ozone is generated even when the temperature drops, but the generation amount is small as shown in the graph of FIG.

以上、結晶の昇温・降温の両方の過程において、（i）から（v）の動作により大気中でオゾンを発生させることができるが、本発明者等の実験では、結晶温度の上昇時の方がオゾン発生量が格段に多くなることが実証された。   As described above, ozone can be generated in the atmosphere by the operations (i) to (v) in both the temperature rising and falling processes of the crystal. It was proved that the amount of ozone generation was significantly increased.

また、温度上昇時その温度勾配を大きくする程、即ち急激な温度変化を与える程オゾン生成効率が向上することも判明した。   It has also been found that the ozone generation efficiency improves as the temperature gradient increases, that is, as the temperature changes more rapidly.

以上は、結晶の負の電気面を上側（大気側）に向けて配置した場合について説明したが、結晶を逆にして正の電気面を上側に向けて置いた場合は、温度上昇時と降下時で逆の現象が生じる。即ち温度降下段階でオゾン生成効率が良くなるが、温度降下の勾配はそれほど急峻にできないので、通常は負の電気面を上にして用いるのが効率的である。   The above describes the case where the negative electrical surface of the crystal is placed upward (atmosphere side), but when the crystal is reversed and the positive electrical surface is placed upward, the temperature rises and falls Sometimes the opposite phenomenon occurs. That is, the ozone generation efficiency is improved at the temperature drop stage, but the gradient of the temperature drop cannot be so steep, so it is usually efficient to use the negative electrical surface upward.

一般に、オゾン生成量は気体圧が高い程多くなるが、衝突する荷電粒子の平均自由行程も小さくなるので、オゾン生成領域は圧力の増加に伴って狭くなる。従ってオゾンの使用目的に応じて適当な気体圧を選定すれば良く、また必要に応じて気体の攪拌機能などを付加して広域的にオゾン発生を促すようにしても良い。   In general, the ozone generation amount increases as the gas pressure increases, but the mean free path of the colliding charged particles also decreases, so the ozone generation region becomes narrower as the pressure increases. Therefore, an appropriate gas pressure may be selected according to the purpose of use of ozone, and a gas stirring function or the like may be added as necessary to promote ozone generation over a wide area.

図３は、前記による結晶の温度上昇時のオゾン発生効率に着目し、筐体内大気を連続的に効率よくオゾン化するようにした実施例である。   FIG. 3 shows an embodiment in which the atmosphere in the housing is continuously and efficiently ozonized by paying attention to the ozone generation efficiency when the temperature of the crystal rises as described above.

図中１は常圧大気を連続的に導入・導出するようにした筐体で、内部に５個の同一定格のタンタル酸リチウム（LiTaO3）の異極像結晶体Ａ Ｂ Ｃ Ｄ Ｅと、それぞれの熱励起手段Ａ’Ｂ’Ｃ’Ｄ’Ｅ’を並べて設置し、各結晶体の加熱・冷却のタイミングを制御回路４によって時間差をもって制御するようにした実施例である。即ち熱励起の位相をずらせることにより、オゾン生成効率の高い状態を連続的に維持することができる。 In the figure, reference numeral 1 denotes a case in which atmospheric pressure is continuously introduced and led out, and five differently rated lithium tantalate (LiTaO 3 ) heteropolar crystal bodies ABCDE, In this embodiment, the thermal excitation means A′B′C′D′E ′ are arranged side by side, and the heating / cooling timing of each crystal is controlled by the control circuit 4 with a time difference. That is, by shifting the phase of thermal excitation, it is possible to continuously maintain a state of high ozone generation efficiency.

図４は、各結晶体Ａ Ｂ Ｃ Ｄ Ｅの熱励起サイクルを示すグラフで、縦軸は結晶の温度、横軸は加熱・冷却の時間で、Ａ”Ｂ”Ｃ”Ｄ”Ｅ”は各結晶体Ａ Ｂ Ｃ Ｄ Ｅの加熱・冷却温度曲線を示す。   FIG. 4 is a graph showing the thermal excitation cycle of each crystal A B C D E, where the vertical axis is the crystal temperature, the horizontal axis is the heating / cooling time, and A ″ B ″ C ″ D ″ E ″ is each The heating / cooling temperature curve of the crystal ABCDE is shown.

各結晶はグラフから判るように、約０．４時間で２００℃まで加熱され約１．６時間で常温に戻るように制御され、それぞれ１２０／５ 分づつの時間差をもって加熱・冷却が繰り返される。これらの加熱・冷却制御は、制御回路４からの信号に基づいてペルチエ素子などの熱励起手段Ａ’Ｂ’Ｃ’Ｄ’Ｅ’を介して各結晶ごとに位相をずらせて制御される。   As can be seen from the graph, each crystal is controlled to be heated to 200 ° C. in about 0.4 hours and returned to room temperature in about 1.6 hours, and heating and cooling are repeated with a time difference of 120/5 minutes. These heating / cooling controls are controlled by shifting the phase of each crystal through thermal excitation means A′B′C′D′E ′ such as a Peltier element based on a signal from the control circuit 4.

このようにすることにより、各結晶が順次オゾン化効率の良い温度上昇過程になるので、筐体内ではオゾン化が連続的に進行し、空気導入管５から導入された大気中の酸素は間断なく連続的にオゾン化され、出口管６から高濃度のオゾン化ガスとして取り出すことができる。   By doing so, since each crystal is in the process of increasing the temperature with good ozonization efficiency, ozonization proceeds continuously in the casing, and oxygen in the atmosphere introduced from the air introduction pipe 5 is not interrupted. It is continuously ozonized and can be taken out from the outlet pipe 6 as a highly concentrated ozonized gas.

図の例では、５個の異極像結晶体を平面状に配置した例について説明したが、さらに多くの結晶体を平面的或いは立体的に配置してもよく、このようにすればより高濃度のオゾンガスを連続的に生成することができる。   In the example of the figure, an example in which five different-polarity crystal bodies are arranged in a planar shape has been described. However, a larger number of crystal bodies may be arranged two-dimensionally or three-dimensionally. Concentration ozone gas can be continuously generated.

また加熱・冷却サイクルの周期や到達上昇温度も、目的とするオゾン濃度や用途に応じて適宜に調整が可能である。   Also, the cycle of the heating / cooling cycle and the ultimate temperature rise can be appropriately adjusted according to the target ozone concentration and application.

尚図３の筐体１が金属製である場合は、発生したオゾンによって酸化・腐食するのを防止するとともに、これによるオゾンの消費を避けるために、点線ｆで示したように内側にフッ素樹脂コーテイングをするか、適宜の酸化防止材を使用するのが望ましい。   3 is made of metal, it is prevented from being oxidized and corroded by the generated ozone, and in order to avoid consumption of ozone by this, as shown by a dotted line f, a fluororesin is provided on the inner side. It is desirable to coat or use an appropriate antioxidant.

尚本発明実施例では、結晶の熱励起手段としてペルチエ素子による加熱・冷却装置を例示したが、ヒーター加熱・マイクロ波加熱やレーザー方式と各種冷媒機構とを組合わせても良く、また結晶自体に電気歪や機械的加圧を与えて分極を乱し電界を発生させる手段を併用することも可能である。   In the embodiment of the present invention, a heating / cooling device using a Peltier element is exemplified as a thermal excitation means of the crystal. However, a heater heating / microwave heating or a laser system and various refrigerant mechanisms may be combined, or the crystal itself may be combined. It is also possible to use a means for disturbing polarization and generating an electric field by applying electrostriction or mechanical pressure.

以上本発明は、予め分極方向を揃えた異極像結晶体を使用し、熱励起によって結晶内に発生する自発分極の変化に追随できない外部の電気的平衡状態の乱れを誘起し、結晶内外に強電界を発生させることがオゾン発生メカニズムの基本概念であり、分極方向が不揃いの中和した結晶では熱励起によってもオゾン生成に有効な高電界や荷電粒子の放電現象は得られない。   As described above, the present invention uses heteropolarized crystal bodies whose polarization directions are aligned in advance, induces disturbance of an external electrical equilibrium state that cannot follow the change in spontaneous polarization generated in the crystal by thermal excitation, and enters and exits the crystal. Generating a strong electric field is a basic concept of the mechanism of ozone generation, and neutralized crystals with uneven polarization directions cannot obtain a high electric field or charged particle discharge phenomenon effective for ozone generation even by thermal excitation.

また、温度変化を付与することが重要であり、高い温度にしても一定温度であれば高電界は発生しないので、充分なオゾン生成効果は得られない。   Moreover, it is important to give a temperature change, and even if the temperature is high, a high electric field is not generated at a constant temperature, so that a sufficient ozone generation effect cannot be obtained.

分極方向の揃った結晶を得るには、結晶成長の段階でその成長過程を制御する方法や結晶を電気的に処理して分極方向を揃える方法などが知られている。   In order to obtain a crystal with a uniform polarization direction, there are known a method of controlling the growth process at the stage of crystal growth, a method of aligning the polarization direction by electrically treating the crystal, and the like.

以上のように本発明では、結晶周辺の気体圧を常圧或いはそれ以上の高い圧力雰囲気中で、結晶の熱励起による電荷不均衡で解離した熱イオン（熱イオン効果）や遊離電子によって発生する軟Ｘ線や、高電界による酸素分子の解離・会合などの複合効果を利用してオゾンを生成するものであるが、結晶周辺の雰囲気が真空と違って常圧またはそれ以上の高圧雰囲気であるので、酸素濃度も高い状態にあり、また荷電粒子の平均自由行程も短くなるので結晶近辺での気体分子との衝突・分子解離も起こり易くなり、分子間衝突による放電・プラズマ作用とも相俟って、酸素分子のオゾン化効率を高めることができたものである。さらに、酸素ガスのみを発生部（筐体内）に導入することにより、オゾン化効率を一層高めることが出きる。   As described above, in the present invention, the gas pressure around the crystal is generated by thermal ions (thermal ion effect) or free electrons dissociated due to charge imbalance due to thermal excitation of the crystal in an atmospheric pressure or higher pressure atmosphere. Ozone is generated by utilizing combined effects such as soft X-rays and dissociation / association of oxygen molecules due to a high electric field, but the atmosphere around the crystal is a high-pressure atmosphere at or above atmospheric pressure unlike vacuum. Therefore, the oxygen concentration is also high, and the mean free path of charged particles is shortened, so collisions with gas molecules and molecular dissociation in the vicinity of the crystal are likely to occur, combined with discharge and plasma action due to intermolecular collisions. Thus, the ozonization efficiency of oxygen molecules has been improved. Furthermore, the ozonization efficiency can be further improved by introducing only oxygen gas into the generating part (inside the casing).

本発明によれば、大型電源・高圧電源や真空設備などを必要としないで、大気中ないしそれ以上の高圧雰囲気中で高濃度のオゾンを生成することができるので、食品や衛生設備の滅菌や殺菌その他空気清浄・表面酸化など幅広い産業分野で有効に利用できる。   According to the present invention, high-concentration ozone can be generated in a high-pressure atmosphere in the atmosphere or higher without the need for a large-scale power source, a high-voltage power source, a vacuum facility, etc. It can be used effectively in a wide range of industrial fields such as sterilization, air purification, and surface oxidation.

本発明方法および装置の基本概念を示す実験例図である。It is an experimental example figure which shows the basic concept of this invention method and apparatus. 図１の実験例における、大気中での結晶の温度変化と生成されるオゾン濃度との関係を示すグラフである。It is a graph which shows the relationship between the temperature change of the crystal | crystallization in air | atmosphere, and the ozone concentration produced | generated in the experiment example of FIG. 本発明の実施例を示す図で、オゾンを連続的に生成する装置の例である。It is a figure which shows the Example of this invention, and is an example of the apparatus which produces | generates ozone continuously. 図３の実施例における各結晶の熱励起サイクルと結晶温度との関係を示すグラフである。It is a graph which shows the relationship between the thermal excitation cycle and crystal temperature of each crystal | crystallization in the Example of FIG.

符号の説明Explanation of symbols

１．筐体
２．分極方向を揃えた異極像結晶体
３．結晶の加熱・冷却ステージ
４．制御回路
５．筐体へのガス導入管
６．筐体からのオゾンガス導出管
７．オゾン濃度測定器
８．９．ガス循環路
１０．１１．１２．１３．開閉弁
Ａ．Ｂ．Ｃ．Ｄ．Ｅ．異極像結晶体 1. Housing 2. 2. Heteropolar crystal with uniform polarization direction 3. Crystal heating / cooling stage 4. Control circuit 5. Gas introduction pipe to the housing 6. Ozone gas outlet pipe from the casing Ozone concentration measuring instrument 8.9. Gas circulation path 10.11.12.13. On-off valve B. C. D. E. Heteromorphic crystal

Claims (3)

常圧以上の大気雰囲気中に、分極の向きを一方向に揃えた異極像結晶体を配置し、この異極像結晶体を周期的に加熱・冷却することにより当該結晶体付近の大気中に高電界を発生させ、この高電界よって大気中に発生する軟Ｘ線と、大気中の酸素分子の解離・再結合、との複合作用によって大気中の酸素分子をオゾン化することを特徴とする異極像結晶を用いたオゾン生成方法。   A heteropolar crystal with the direction of polarization aligned in one direction is placed in an atmospheric atmosphere at or above atmospheric pressure, and this heteropolar crystal is periodically heated and cooled in the atmosphere near the crystal. A high electric field is generated, and oxygen molecules in the atmosphere are ozonized by a combined action of soft X-rays generated in the atmosphere by the high electric fields and dissociation / recombination of oxygen molecules in the atmosphere. Ozone generation method using heteropolar image crystals. 常圧以上の大気を封入した筐体内に、分極方向を一方向に揃えた異極像結晶体をその一方の極性側表面が直接大気に接するように配置し、結晶体の他方側にこれを熱励起する手段を設け、この熱励起手段を介して前記結晶体の温度を周期的に昇降させることにより結晶体の周辺に高電界を発生させ、この高電界による荷電粒子の挙動を利用して筐体内の大気中にオゾンを生成させることを特徴とする異極像結晶を用いたオゾン生成装置。   A heteropolar crystal with the polarization direction aligned in one direction is placed in a case filled with atmospheric pressure or higher so that the surface on one polar side is in direct contact with the atmosphere, and this is placed on the other side of the crystal. A means for thermal excitation is provided, and a high electric field is generated around the crystal body by periodically raising and lowering the temperature of the crystal body through the thermal excitation means, and the behavior of charged particles by this high electric field is utilized. An ozone generator using a heteropolar image crystal, characterized in that ozone is generated in the atmosphere in a housing. 異極像結晶体を筐体内に複数個配置し、各結晶体をその温度昇降周期の位相をずらせて各別に熱励起することを特徴とする請求項２に記載の異極像結晶を用いたオゾン生成装置。   The heteropolar image crystal according to claim 2, wherein a plurality of heteropolar image crystals are arranged in a housing, and each crystal is thermally excited separately by shifting the phase of its temperature rise / fall cycle. Ozone generator.
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US7558373B2 (en) * 2004-03-30 2009-07-07 The Doshisha X-ray generator employing hemimorphic crystal and ozone generator employing it
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JP5057329B2 (en) * 2007-10-30 2012-10-24 国立大学法人京都大学 X-ray generator using heteropolar crystal
ES2569122T3 (en) 2009-08-07 2016-05-06 The Regents Of The University Of California Apparatus for producing X-rays for use in imaging
WO2013058342A1 (en) * 2011-10-18 2013-04-25 株式会社Ｂｓｒ Charged particle emission device and x-ray generator using the device
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US6432279B1 (en) * 1999-09-07 2002-08-13 Anthony A. Zanta Method and apparatus for ozone generation and contaminant decomposition
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